Methods of atomic-layer deposition of hafnium oxide/erbium oxide bi-layer as advanced gate dielectrics

ABSTRACT

Provided is a two-step ALD deposition process for forming a gate dielectric involving an erbium oxide layer deposition followed by a hafnium oxide layer deposition. Hafnium oxide can provide a high dielectric constant, high density, large bandgap and good thermal stability. Erbium oxide can act as a barrier against oxygen diffusion, which can lead to increasing an effective oxide thickness of the gate dielectric and preventing hafnium-silicon reactions that may lead to higher leakage current.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Continuation application of U.S. patent application Ser. No.13/480,302, filed on May 24, 2012, which is herein incorporated byreference for all purposes.

FIELD OF THE INVENTION

This invention relates generally to semiconductor devices and, moreparticularly, to methods for forming date dielectrics and devices formedusing these methods.

BACKGROUND OF THE INVENTION

As integrated circuit feature sizes decrease, other device dimensionsalso need to scale down to maintain the proper device operation. Forexample, as gate conductor widths are being reduced, the thickness ofthe gate dielectric needs to decrease to provide proper capacitance tocontrol the transistor.

To meet the requirements of sub-100 nm devices, an equivalent oxidethickness (EOT) of less than 1.5 nm is needed. When SiO₂ is used as thegate dielectric, it is difficult to maintain its dielectric propertybelow about 2 nm thickness due to the high tunneling leakage.

High-k materials, i.e., dielectric materials having a higher dielectricconstant (k) than that of SiO₂ (k˜3.9), can provide a high capacitancewith higher thickness, and thus have been studied as a replacement forSiO₂. For example, a high-k value of 20, which can be obtained withvarious transition metal oxides such as hafnium oxide, can allow aboutfive times thicker structures than a SiO₂ film with similar capacitancevalue. The thicker gate dielectric layer of high-k material can reducetunneling leakage current through the gate, enabling sub-100 nm MOSFETdevices.

The fabrication of high-k gate dielectric layers can provide difficultyin realizing the full benefits of the high dielectric constant. Forexample, processing high-k dielectric layers in the presence of oxygenat elevated temperatures, e.g., high-k deposition or subsequent annealprocesses, can form a SiO₂ interfacial layer between the siliconsubstrate and high-k layer. The SiO₂ interfacial layer can increase theeffective oxide thickness, reducing the capacitance of the gatedielectric layer. Further, high-k gate dielectrics can contain a greaternumber of bulk traps and interface traps than thermally growth SiO₂ gatedielectrics. The traps can degrade the device performance, such assub-threshold slope, threshold voltage, flatband voltage shift, andFrenkel-Poole tunneling leakage.

Thus there is a need to develop improved methods and structuresinvolving high-k gate dielectrics and related semiconductor devices.

SUMMARY OF THE DISCLOSURE

In some embodiments, the provided are methods to form a gate dielectricincluding a bi-layer of hafnium oxide on erbium oxide. Hafnium oxide canprovide high dielectric constant, high density, large bandgap and goodthermal stability. Erbium oxide can be a passivating interfacial layer,acting as a barrier against oxygen diffusion, which can lead toincreasing effective oxide thickness of the gate dielectric andpreventing hafnium-silicon reactions which can lead to higher leakagecurrent.

In some embodiments, provided is a two-step deposition process involvingan interface layer deposition followed by a bulk layer deposition. Inthe interface layer deposition process, an erbium precursor togetherwith an oxidant precursor can be used to deposit an interface layer oferbium oxide. In the bulk layer deposition process, a hafnium precursortogether with an oxidant precursor can be used to deposit a bulk layerof hafnium oxide. In the context of the present invention, an erbiumprecursor includes an erbium containing precursor, such as a precursorthat containing erbium element. Similarly, a hafnium precursor includesa hafnium containing precursor, such as a precursor that containinghafnium element.

In some embodiments, an ALD (atomic layer deposition) process isprovided including an interface layer deposition followed by a bulklayer deposition. In some embodiments, an ALD process is provided,including depositing an erbium oxide layer by a first number of cyclesusing an oxidant and an erbium precursor, followed by a second number ofcycles using the same or different oxidant and a hafnium precursor.

In some embodiments, provided is a gate dielectric, and a semiconductordevice utilizing the gate dielectric, including a bi-layer of hafniumoxide on erbium oxide. Bi-layer of hafnium oxide on erbium oxide canhave fewer defects, offering improved electrical properties, suitablefor high k gate dielectrics in semiconductor device applications.

BRIEF DESCRIPTION OF THE DRAWINGS

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The drawings are not to scale and the relative dimensionsof various elements in the drawings are depicted schematically and notnecessarily to scale.

The techniques of the present invention can readily be understood byconsidering the following detailed description in conjunction with theaccompanying drawings, in which:

FIG. 1 illustrates an illustrative metal-oxide semiconductor fieldeffect transistor (MOSFET) device according to some embodiments of thepresent invention.

FIGS. 2A-2B illustrate a fabrication sequence for an illustrative metalgate electrode according to some embodiments of the present invention.

FIG. 3 illustrates a flow chart of an ALD deposition of metal oxidedielectric materials according to some embodiments of the presentinvention.

FIGS. 4A-4F illustrate an illustrative process flow schematic of an ALDdeposition of an illustrative hafnium oxide according to someembodiments of the present invention.

FIG. 5 illustrates an illustrative gate dielectric according to someembodiments of the present invention.

FIG. 6 illustrates an illustrative flowchart for forming a gatedielectric layer according to some embodiments of the present invention.

FIG. 7 illustrates an illustrative flowchart for forming a semiconductordevice according to some embodiments of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A detailed description of one or more embodiments is provided belowalong with accompanying figures. The detailed description is provided inconnection with such embodiments, but is not limited to any particularexample. The scope is limited only by the claims and numerousalternatives, modifications, and equivalents are encompassed. Numerousspecific details are set forth in the following description in order toprovide a thorough understanding. These details are provided for thepurpose of example and the described techniques may be practicedaccording to the claims without some or all of these specific details.For the purpose of clarity, technical material that is known in thetechnical fields related to the embodiments has not been described indetail to avoid unnecessarily obscuring the description.

In some embodiments, methods, and structures fabricated from themethods, to form a hafnium oxide gate dielectric are provided. Thepresent hafnium oxide gate dielectric can have a bulk hafnium oxide withlow defect density positioned on an interfacial layer of erbium oxidewith improved interface trap charge density. In addition, the interfaceerbium oxide can reduce the formation of interface SiO₂, for example, byacting as an oxygen diffusion barrier, reducing the equivalent oxidethickness of the gate dielectric.

In some embodiments, the present hafnium oxide gate dielectric can beformed by a two-step deposition process, which includes an interfacelayer deposition followed by a bulk layer deposition. In the interfacelayer deposition process, an erbium-containing precursor can be used todeposit an erbium oxide layer. Erbium oxide can be a passivatinginterfacial layer, acting as a barrier against oxygen diffusion whichcan lead to increasing effective oxide thickness of the gate dielectric,and preventing hafnium-silicon reactions which can lead to higherleakage current. In the bulk layer deposition process, a hafniumprecursor can be used to deposit a hafnium oxide layer. Hafnium oxidecan provide high dielectric constant, high density, large bandgap, andgood thermal stability.

Advances in semiconductor processing have demanded ever-increasing highfunctional density with continuous size scaling. This scaling processhas led to the adoption high-k gate dielectrics and metal gateelectrodes in metal gate stacks in semiconductor devices.

High-k gate dielectrics can offer a way to scale down the thickness ofthe gate dielectric with acceptable gate leakage current. The use ofhigh-k gate dielectrics is often accompanied by a metal gate electrode,since thin gate dielectric layers may cause poly depletion, affectingthe device operation and performance. Metal gate electrodes further havean advantage of higher electrical conductance, as compared to polygates, and thus can improve signal propagation times.

The manufacture of high-k dielectric devices entails the integration andsequencing of many unit processing steps, with potential new processdevelopments, since in general, high-k gate dielectrics are much moresensitive to process conditions than silicon dioxide. For example,interface traps and interface oxide formation can adversely affect theperformance of the high-k gate structures.

Industry continues to search for new dielectric materials that exhibithigh k value (i.e. dielectric constant) and low leakage, to enablefurther miniaturization of electronic devices. These materials may beused as the dielectric layer in electronic components such ascapacitors, memory cell structures, and other devices. The k value is ameasure of the polarization capability of dielectric materials inresponse to external electrical field, which can be used to storecharges in capacitors. The ability of a dielectric material to storecharge is also conveniently represented by the equivalent oxidethickness (“EOT”). A low EOT implies an increased ability to miniaturizesemiconductor devices. The leakage is a measure of the capacitor'scapability to retain stored charge for a certain period of time. BothEOT and leakage are important parameters for the miniaturization ofelectronic components such as capacitors, memory cell structure andother devices. Typical high-k materials include Al₂O₃ (k ^(˜)9), HfSiO(k ^(˜)5-20), ZrO₂ (k ^(˜)25), HfO₂ (k ^(˜)25), Ta₂O₅ (k ^(˜)26), andTiO₂ (k ^(˜)80).

In some embodiments, hafnium oxide gate dielectric layers can replaceSiO₂ gate dielectric with thinner equivalent oxide thickness (EOT)required for lower transistor operating voltages and smaller transistordimensions. Further, hafnium oxide layer can have minimum SiO₂interfacial layer. During the formation of hafnium oxide on a siliconlayer, an interface layer of SiO₂ could be formed in addition to thehafnium oxide, resulting in two layers in series with each other. Thetwo-layer equivalent oxide thickness would much higher than that of thehafnium oxide layer alone, and depending on the thickness of the SiO₂interfacial layer, can be determined or limited by the SiO₂ interfaciallayer thickness.

In some embodiments, provided is a two step deposition process to form agate dielectric layer, including depositing an erbium oxide layer beforedepositing a layer of hafnium oxide. The present two step depositionprocess can provide a gate dielectric layer having hafnium oxideproperties with minimum SiO₂ formation, and a high quality interface tomaintain high channel carrier mobility for the semiconductor device.

FIG. 1 illustrates an illustrative metal-oxide semiconductor fieldeffect transistor (MOSFET) device according to some embodiments of thepresent invention. The device 100 can be incorporated into integratedcircuits, which can also include various interconnects for connectingmultiples devices including the device 100. The device 100 may include asubstrate 180, which may be made from single crystal silicon. Othersubstrate materials include silicon-germanium. A gate stack may befabricated on the substrate 180. The gate stack is shown to include ahigh-k gate dielectric layer 110, gate electrode layer 120 provided overthe gate dielectric layer 110, and gate conductor layer 130 providedover the gate electrode layer 120. The gate electrode layer 120 can be apolysilicon gate layer or a metal gate layer. The device 100 is isolatedfrom other devices by isolation regions 160, such as shallow trenchisolation or local oxidation of silicon (LOCOS) isolation. The device100 also includes spacers 140 and source and drain regions 150. Thesource and drain regions 150 are doped, for example, with arsenic,phosphorous, boron or other suitable materials, which are selected basedon the desired transistor characteristics, using a self-aligning ionimplantation process in substrate 180 or other suitable process. Othercomponents can be included, such as n-well or p-well region, dependingon the type of the semiconductor device.

The gate electrode layer 120 is deposited on the high-k dielectric layer110 and includes aluminum, polysilicon, or other suitable conductivematerials (e.g., TiN, TaN, HfN, RuN, WN, W, MoN, TaSiN, RuSiN, WSiN,HfSiN, TiSiN, etc). The spacers 140 are deposited on the sides of gateelectrode layer 120, high-k dielectric layer 110, and can include SiO₂,Si₃N₄, TEOS or other suitable dielectric material. The spacers 140isolate the gate electrode 120 and high-k dielectric layer 110 from thesource and drain regions 150.

High-k dielectric layer 110 includes a high-k dielectric material ofHfO₂. High-k dielectric layer 110 provides an equivalent oxide thickness(EOT) that allows increased performance and reduced transistor devicesize while not increasing tunneling leakage current through the gate. Insome embodiments, the high k dielectric includes a bi-layer of hafniumoxide on erbium oxide. Hafnium oxide can provide high dielectricconstant, high density, large bandgap and good thermal stability. Erbiumoxide can be a passivating interfacial layer, acting as a barrieragainst oxygen diffusion which can lead to increasing effective oxidethickness of the gate dielectric, and preventing hafnium-siliconreactions which can lead to higher leakage current.

FIGS. 2A-2B illustrate a fabrication sequence for an illustrative metalgate electrode according to some embodiments of the present invention.In FIG. 2A, blanket layers of gate dielectric 210, metal gate layer 220and gate conductor layer 230 are deposited on a substrate 280. Thesubstrate 280 can be previously processed, for example, to form devicewell and isolation regions. The structure shown is illustrative, andother configurations can be used, such as a single metal gate layerinstead of a metal gate layer 220 and a gate conductor layer 230, and agate dielectric layer stack including a high-k dielectric layer on asilicon dioxide pedestal layer instead of a single gate dielectric layer210.

The gate dielectric layer 210 can be formed of a bi-layer of hafniumoxide on erbium oxide, fabricated using two step deposition with erbiumcontaining precursor and hafnium containing precursor. The bi-layerhafnium oxide/erbium oxide gate dielectric can improve the performancecharacteristics of semiconductor devices. In some embodiments, thethickness of the gate dielectric is less than about 10 nm, andpreferably less than about 5 nm. The thickness of the erbium oxide layercan be less than about 2 nm, such as less than about 1 nm. The thicknessof the hafnium oxide layer can be less than about 4 nm, such as lessthan about 2 nm. The gate dielectric layer 210 can be formed by variousdeposition techniques, such as an ALD process.

Disposed on the gate dielectric layer 210 is a metal gate layer 220together with a gate conductor layer 230. Alternatively, the gateconductor layer 230 can be omitted, leaving only a metal gate layer 220.The metal gate layer 220 typically includes a first metal, and the gateconductor 230 can either include a poly silicon or a second metal,different from the first metal. In some embodiments, the metal gatelayer 220 is a metal-containing layer, having a metal component togetherwith other combination of materials.

The metal gate layer 220 can include a refractory metal or a nitride ofa refractory metal, such as titanium nitride. Alternatively, the metalgate layer 220 can include other metals, including WN, TaN, Mo, RuO₂, orNiSi. The thickness of the metal gate layer 220 can be less than about20 nm with the gate conductor layer, or can be less than about 200 nmwithout a gate conductor layer.

The gate conductor layer 230 can include silicon, such as doped polysilicon. Alternatively, the gate conductor layer 230 can include asecond metal, different from the first metal in the metal gate layer220. In addition, the gate conductor can be omitted. The thickness ofthe gate conductor can be less than 200 nm.

The metal gate layer 220 and gate conductor layer 230 can be formed byany methods, such as atomic layer deposition (ALD), physical vapordeposition (PVD), chemical vapor deposition (CVD), and spin coating.

FIG. 2B shows a device having the gate conductor layer 230, metal gate220, and gate dielectric 210. Any patterning process can be used tofabricate this structure, for example, lithography patterning processusing photoresist mask and dry or wet etching may be used. The layerscan be patterned using a plasma etch process or a wet etch process.

After the completion of the metal gate electrode, the substrate can befurther processed to form active devices and circuits. For example,additional steps of implanting dopants to form source and drainstructures 250, forming gate spacers 240, and shallow junctions.Interconnect metal lines can be included for connecting multiple activedevices to form an integrated circuit. There can be silicide regions(not shown) on the gate conductor layer 230 for improving contactresistance. The device shown is an illustrative planar deviceconfiguration, and other device configurations are also within the scopeof the present invention, such as tri-gate transistor configurations,fin-FET configurations, or different types of transistors or devices.

In some embodiments, provided is an ALD (atomic layer deposition)process including an interface layer deposition followed by a bulk layerdeposition. In some embodiments, an ALD process is provided, includingdepositing an erbium oxide layer by a first number of cycles using aprecursor having erbium component (such as erbium cyclopentadienyl (Cp)complex type precursors or erbium beta-diketonate chelate typeprecursors), followed by depositing a hafnium oxide layer by a secondnumber of cycles using a precursor having hafnium component (such ashafnium amino type precursors). Fewer defects and less oxygen diffusionto the silicon interface can provide a gate dielectric layer of hafniumoxide on erbium oxide with improved electrical properties, suitable forhigh k gate dielectrics in semiconductor device applications.

ALD as used herein refers to the sequential introduction of two or morereactive compounds to deposit a layer of material on a substratesurface. The two, three or more reactive compounds may alternatively beintroduced into a reaction zone of a deposition chamber. Usually, eachreactive compound is separated by a time delay to allow each compound toadhere and/or react on the substrate surface. In some embodiments, afirst precursor or compound A is pulsed into the reaction zone of adeposition chamber (e.g., ALD chamber) followed by a first time delay.Next, a second precursor or compound B is pulsed into the reaction zonefollowed by a second delay. During each time delay a purge gas, such asargon or nitrogen, may be pulsed or otherwise provided into thedeposition chamber to purge the reaction zone or otherwise remove anyresidual reactive compound or by-products from the reaction zone orother surfaces. Alternatively, the purge gas may flow continuouslythroughout the deposition process so that only the purge gas flowsduring the time delay between pulses of reactive compounds. The reactivecompounds are alternatively pulsed until a desired film or filmthickness is formed on the substrate or deposition. In either scenarioof a continuous or intermittent purge gas flow, the ALD process ofpulsing compound A, purge gas, pulsing compound B, and purge gas is anALD cycle. An ALD cycle can start with either compound A or compound Band continue the respective order of the ALD cycle until achieving afilm with the desired thickness. In some embodiments, a first precursoror compound A is pulsed into the reaction zone of a deposition chamber(e.g., ALD chamber) followed by a first time delay. Next, a secondprecursor or compound B is pulsed into the reaction zone followed by asecond delay. Next, a third precursor or compound C is pulsed into thereaction zone followed by a third delay. During each time delay a purgegas, such as argon or nitrogen, may be pulsed or otherwise provided intothe deposition chamber to purge the reaction zone or otherwise removeany residual reactive compound or by-products from the reaction zone orother surfaces. Alternatively, the purge gas may flow continuouslythroughout the deposition process so that only the purge gas flowsduring the time delay between pulses of reactive compounds. The reactivecompounds are alternatively pulsed until a desired film or filmthickness is formed on the substrate or deposition surface. In eitherscenario of a continuous or intermittent purge gas flow, the ALD processof pulsing compound A, purge gas, pulsing compound B, purge gas, pulsingcompound C, and purge gas is an ALD cycle. Alternatively, the ALDprocess of pulsing compound A, purge gas, pulsing compound B, purge gas,pulsing compound C, purge gas, pulsing compound B, and purge gas is anALD cycle. An ALD cycle can start with either compound A, compound B, orcompound C and continue the respective order of the ALD cycle untilachieving a film with the desired thickness.

A “pulse” as used herein is intended to refer to a quantity of aparticular compound that is intermittently or non-continuouslyintroduced into a reaction zone of a processing chamber. The quantity ofa particular compound within each pulse may vary over time, depending onthe duration of the pulse. The duration of each pulse is variabledepending upon a number of factors such as, for example, the volumecapacity of the deposition chamber employed, the vacuum system coupledthereto, and the volatility/reactivity of the particular compounditself. A “half-reaction” as used herein is intended to refer to a pulseof precursor step followed by a purge step.

FIG. 3 illustrates a flow chart of an ALD deposition of metal oxidedielectric materials according to some embodiments of the presentinvention. In step 300, a metal precursor is pulsed into the reactionzone. A portion of the precursor adsorbs onto the surface at reactivesites. In step 302, the remainder of the precursor is purged from thereaction zone. In step 304, an oxidant is then pulsed into the reactionzone to react with the adsorbed precursor and form a metal oxidedielectric material. In step 305, the remainder of the oxidant is purgedfrom the reaction zone. In step 306, this sequence is repeated until thedesired thickness of the metal oxide dielectric material is formed.

In some embodiments, provided are methods of forming a bi-layer ofhafnium oxide/erbium oxide gate dielectric using atomic layer deposition(ALD). Some of the materials and/or layers of the erbium oxide andhafnium oxide layer may be deposited or otherwise formed using a varietyof deposition techniques, but in many embodiments described herein, allof the materials and/or layers of erbium oxide and hafnium oxide layersmay be deposited using thermal ALD processes and/or plasma-enhanced ALD(PE-ALD). In some embodiment, an interfacial erbium oxide can be formedby utilizing an erbium precursor and an oxygen-containing oxidizeragent, such as water, ozone, atomic oxygen, or oxygen plasma, togetherwith a bulk hafnium oxide formed by utilizing a hafnium precursor and anoxygen based oxidizer agent.

The ALD processes for depositing or otherwise forming gate dielectricmaterials are typically conducted in a deposition chamber, such as anALD chamber. The deposition chamber may maintain an internal pressure ofless than 760 Torr, such as within the range from about 10 mTorr toabout 10 Torr, such as from about 100 mTorr to about 1 Torr, forexample, about 350 mTorr. The temperature of the memory device, thesubstrate, or the substrate carrier/pedestal is usually maintainedwithin the range from about 50° C. to about 1,000° C., such as fromabout 100° C. to about 500° C., such as from about 200° C. to about 400°C., or such as from about 250° C. to about 300° C.

The erbium and/or hafnium precursor can be pulsed, introduced, orotherwise provided into the deposition chamber at a flow rate within therange from about 0.1 sccm to about 200 sccm, such as from about 0.5 sccmto about 50 sccm, from about 1 sccm to about 30 sccm, for example, about10 sccm. The erbium and/or hafnium precursor can be provided along witha carrier gas, such as argon or nitrogen. The carrier gas may have aflow rate within the range from about 1 sccm to about 300 sccm, such asfrom about 2 sccm to about 80 sccm, from about 5 sccm to about 40 sccm,for example, about 20 sccm. In general, flow rates depend on the size ofthe chamber and size of the substrate, and one having ordinary skill inthe art would be able to scale these values up or down based ondifferent sizes of chamber or substrates.

The erbium and/or hafnium precursor may be pulsed or otherwise providedinto the deposition chamber at a rate within a range from about 0.01seconds to about 60 seconds, depending on the particular processconditions, precursors or desired composition of the deposited erbium orhafnium oxide materials.

In some embodiments, the erbium precursor is an erbium organic precursorincluding an organic ligand. For example, the erbium precursor caninclude one or more of tri(cyclopentadienyl) erbium (Er(Cp)₃),tri(methylcyclopentadienyl) erbium (Er(MeCp)₃),tri(ethylcyclopentadienyl) erbium (Er(EtCp)₃),tri(isopropylcyclopentadienyl) erbium (Er(IpCp)₃),tri(nbutylcyclopentadienyl) erbium (Er(nBuCp)₃), andtris-tetramethylheptanedionate erbium (Er(thd)₃).

In some embodiments, the hafnium precursor is a hafnium inorganicprecursor, such as hafnium chloride (HfCl₄), hafnium iodine (Hfl₄), oranhydrous hafnium nitrate (Hf(NO₃)₄). In some embodiments, the hafniumprecursor is a hafnium organic precursor including an organic ligand.For example, the metal source can be a hafnium precursor which is atetrakis(dialkylamino)hafnium compound, such as tetrakis(dimethylamino)hafnium ((Me₂N)₄Hf or TDMAH), tetrakis(diethylamino) hafnium ((Et₂N)₄Hfor TDEAH), or tetrakis(ethylmethylamino) hafnium ((EtMeN)₄Hf or TEMAH).

The erbium and/or hafnium precursor can be dispensed into a depositionchamber by introducing a carrier gas through an ampoule containing theorganic precursor. An ampoule can include a container, a bubbler, acanister, a cartridge, or other container used for storing, containing,or dispersing chemical precursors. For example, the ampoule can containa liquid precursor (e.g., TDMAH or TDEAH) and be part of a liquiddelivery system containing injector valve system used to vaporize theliquid precursor with a heated carrier gas. Generally, the ampoule canbe heated to a temperature of about 100° C. or less, such as within arange from about 30° C. to about 180° C., for example, about 50° C.Alternatively, the precursor can be in gaseous form, and can bedelivered directly to the deposition. The precursor can be in solidform, such as HfCl₄, and can be vaporized from solid to vapor, forexample, upon heating to above 150 C to achieve relatively high vaporpressure.

The oxidizing agent (e.g., O₂, O₃, H₂O) may be pulsed, introduced, orotherwise provided into the deposition chamber at a flow rate within arange from about 0.01 seconds to about 60 seconds, depending on theparticular process conditions, oxygen source gas or oxidizing agent ordesired composition of the deposited metal oxide material. In someembodiments, such as for forming a metal-poor oxide material, theoxidizing agent may be pulsed, introduced, or otherwise provided intothe deposition chamber at a rate within a range from about 0.001 secondsto about 1 second, such as from about 0.001 seconds to about 0.1seconds, for example, about 0.05 seconds. The oxidizer may be deliveredto the process chamber by known methods. For example, a water vaporgenerator is used to generate water vapor and deliver (or pulse) it tothe process chamber as the oxidizer. Ozone may be formed inside oroutside of the deposition chamber, such as the ALD chamber. In someembodiments, the oxidizing agent contains ozone formed by an ozonegenerator positioned outside of the deposition chamber. Ozone isgenerated and then flowed or directed into the deposition chamber andexposed along with the metal source gas to the substrate surface. Insome embodiments, the oxidizing agent contains ozone formed by a plasmagenerated within the interior of the deposition chamber. Oxygen gasflowed or directed into the deposition chamber, then ignited or formedinto ozone and/or atomic oxygen before being sequentially exposed alongwith the precursor to the substrate surface.

The chamber may be purged between oxidizing and precursor exposure, andbetween repeating cycles of exposure to the oxidizer and precursor, andthe cycles may be repeated a desired number of times. The purgingprocess may use an inert gas, for example, such as N₂, or Ar. The purgetime may be any desired time for removing excess reactant from thechamber.

A carrier gas or a purge gas can be provided at the same time as thehafnium precursor and/or the oxidant precursor, but can be also providedbetween the pulses of the metal precursor (e.g., erbium or hafnium)and/or the oxidant precursor. The carrier gas or purge gas can flowcontinuously during the ALD process or can be intermediately and/orsequentially pulsed, introduced, or otherwise provided during the ALDprocess. The carrier gas or purge gas may be pulsed, introduced, orotherwise provided into the deposition chamber at a rate within a rangefrom about 1 second to about 60 seconds, depending on the particularprocess conditions, source gases, or desired composition of thedeposited metal oxide material. In some embodiments, the carrier gas ora purge gas may be pulsed, introduced, or otherwise provided into thedeposition chamber at a rate within a range from about 1 second to about30 seconds, such as from about 2 seconds to about 20 seconds, forexample, about 10 seconds or about 15 seconds. Other purging times canbe used.

The carrier gas or purge gas may contain nitrogen, argon, helium,mixtures thereof, or combinations thereof. The carrier gas or the purgegas may be sequentially pulsed, introduced, or otherwise provided aftereach pulse of the metal precursor and each pulse of the oxidizing agentduring the ALD cycle. The pulses of purge gas or carrier gas aretypically pulsed, introduced, or otherwise provided at a flow ratewithin a range from about 2 standard liters per minute (slm) to about 22slm, such as about 10 slm. Other purging flows can be used.

Once the desired number of cycles of alternating exposure to theoxidizer and precursor are carried out, a post-deposition anneal may beperformed to densify the film stack. The post-deposition anneal may be ahigh temperature bake, a post-oxidation anneal, or a high temperatureanneal in the presence of a non-oxidizing gas, such as N₂. In someembodiments, the substrate temperature during the post-deposition annealis in the range of about 500-1000° C., such as about 550-800° C.Illustrative post-deposition anneals include exposure to NO at about600° C. or exposure to N2 at about 800° C. The anneal may be performedfor any desired amount of time. By way of example and not limitation,the anneal may be performed for about 30 seconds up to 30 minutes, orabout 5-20 minutes, for example about 10 minutes. In some embodiments, alow temperature post-deposition anneal may be carried out, for exampleat a temperature below about 500° C., such as about 250-450° C. In someembodiments, a flow rate of up to about 20 slm, for example about 0.1-5slm, may be used for the oxidation gas or non-oxidizing gas.

FIGS. 4A-4F illustrate an illustrative process flow schematic of an ALDdeposition of an illustrative hafnium oxide according to someembodiments of the present invention. In FIG. 4A, a substrate 400 isprovided in a process chamber. The substrate can be a semiconductorsubstrate such as a silicon substrate. In some embodiments, thesubstrate 400 is already processed to form appropriate structures forsemiconductor devices. For example, n well and p well regions can beformed for forming a foundation for p-type and n-type transistors. InFIG. 4B, the substrate surface is conditioned for ALD deposition, forexample, by providing an OH terminated surface 410. The OH surface 410can be prepared by exposing the substrate to water.

In FIG. 4C, hafnium chloride (HfCl₄) precursor 420 is introduced to theprocess chamber. In FIG. 4D, hafnium chloride precursor reacts with theOH surface to form hafnium oxide bonding 430. The un-reacted hafniumchloride precursor is purged from the chamber. In FIG. 4E, water 440 isintroduced to the process chamber. In FIG. 4F, water molecules reactwith hafnium surface 430 to conditioning the substrate surface to OHterminated surface 410*. The process cycle continues, for example, byintroducing hafnium chloride precursor to react with OH terminatedsurface.

The above description shows an example of ALD hafnium oxide depositionusing HfCl₄ precursor and H₂O oxidant. The behaviors of other precursorsand oxidants are similar, such as HfCl₄ with ozone, or an erbiumprecursor with water or ozone oxidant.

In some embodiments, provided are methods of forming an interface erbiumoxide layer on a silicon substrate. The interface erbium oxide can beformed by reacting an erbium precursor, such as erbium cyclopentadienyl(Er(Cp)₃) with water (or other oxygen containing chemicals, such asozone). Erbium oxide is chemically stable in contact with silicon, andhas a higher dielectric constant than silicon oxide (k ˜10-14 ascompared to 3.9 of silicon). Erbium oxide film can be denser uponannealing. For example, during a number of ALD cycles of a first ALDerbium oxide deposition, an oxidant step, e.g., using water, ozone,atomic oxygen or plasma excited oxygen, can be provided to engineer theerbium oxide interface layer of the gate dielectric with the siliconsubstrate, such as reducing oxidation of the silicon surface or reducinginterface traps at the silicon interface.

A hafnium oxide layer then can be formed on the interface erbium oxidelayer, by reacting a hafnium precursor with an oxidant, which can be thesame or different oxidant used in the formation of the interface erbiumoxide layer). For example, for ALD reaction using HfCl₄ precursor and O₃oxidant, the flow rate and concentration of ozone can be optimized toachieve hafnium oxide layer with good electrical performance. Forexample, low concentration and low flow of ozone can be used, followedby high concentration and high flow to obtain less ozone diffusion tothe interface with high oxygen concentration in the bulk hafnium oxidelayer.

In some embodiments, provided are methods to form a bi-layer gatedielectric for a semiconductor device. The method includes providing asilicon-containing substrate; depositing a first layer of erbium oxideon the substrate using an ALD process including alternating anerbium-containing precursor and an oxygen-containing precursor; anddepositing a second layer of hafnium oxide on the first layer using anALD process including alternating the hafnium-containing precursor andan oxygen-containing precursor or a plasma oxygen precursor. The ALDprocess for depositing the first layer can have between 5 to 20 ALDcycles, or for less than 3 monolayer thickness, or for less than 1 nmthickness. The ALD process for depositing the second layer can havebetween 5 to 40 ALD cycles, or for less than 10 monolayer thickness, orfor less than 2 nm thickness.

In some embodiments, provided are methods to form a gate dielectric,including depositing a first layer of erbium oxide by an ALD processthat uses an erbium precursor, followed by depositing a second layer ofhafnium oxide by an ALD process that uses a hafnium precursor.

In some embodiments, an ALD process to form a gate dielectric isprovided, including depositing a first number of cycles with an erbiumprecursor and a first oxidant, followed by a second number of cycleswith a hafnium precursor and a second oxidant, which can be the same ordifferent from the first oxidant.

In some embodiments, provided are methods to form a semiconductordevice, including forming a bi-layer of erbium oxide/hafnium oxide gatedielectric on a semiconductor substrate, followed by forming atransistor structure on the gate dielectric. The gate dielectric can beformed by a two step ALD deposition process, including a first step ofusing an erbium precursor and a second step of using a hafniumprecursor.

FIG. 5 illustrates an illustrative gate dielectric according to someembodiments of the present invention. A hafnium oxide layer 540 isdisposed on an erbium oxide layer 530, which is disposed on a siliconsubstrate 520. The hafnium oxide layer 540 may be deposited by an ALDprocess, utilizing a hafnium precursor and an oxygen based oxidant. Theerbium oxide layer 530 may be deposited by an ALD process, utilizing anerbium precursor and an oxygen based oxidant. In some embodiments, thetwo oxide layers are distinct and are deposited in sequence. In someembodiments, the two oxide layers are deposited in a same chamber withthe hafnium oxide layer immediately follows the erbium oxide layer, forexample, by switching the precursor from erbium precursor to hafniumprecursor.

FIG. 6 illustrates an illustrative flowchart for forming a gatedielectric layer according to some embodiments of the present invention.In operation 600, a semiconductor substrate is provided. The substratecan be a silicon substrate that can include one or more processing stepsperformed thereon.

In operation 610, the substrate is prepared for ALD process, includingbeing heated, for example by heating a pedestal on which the substrateis mounted in an ALD chamber. In this way, a pedestal temperature ismaintained for an ALD deposition process so that the hafnium oxidelayers can be deposited. For example, the pedestal temperature can beless than or equal to about 350 or 400° C.

After preparing the substrate, an erbium oxide layer is formed using ALDprocess. In operation 620, a first few cycles of the ALD process, forexample, between about 5 to 20 cycles, is used to form an erbium oxidelayer using an erbium precursor together with an oxidant.

As mentioned above, ALD is a multi-step process used to depositsemiconductor layers. An ALD-deposited layer typically includes multiplecycles to deposit a layer of a desired thickness, so the process isrepeated until the desired layer thickness has been deposited.

In a typical ALD metal oxide formation, a first reagent is introduced to(e.g., flowed onto) a substrate by introducing the first reagent into anALD chamber. The first reagent can be an erbium-containing precursorthat is used to form an erbium oxide. For example, the first reagent canbe an erbium precursor, such as Er(Cp)₃, Er(MeCp)₃, Er(EtCp)₃,Er(iPrCp)₃, Er(nBuCp)₃, or Er(thd)₃.

The excess (unreacted portion) of the first reagent is purged, forexample by purging the ALD chamber to remove excess precursor. The purgeduration can be less than or equal to about 60 seconds.

A second reagent is introduced to the substrate. The second reagentcombines with the first reagent to form the erbium oxide. The secondreagent is an oxidizer, for example water vapor, alcohol vapor, oxygen,ozone, or plasma oxygen. The second reagent forms an oxide of the metalcontained in the first reagent (the precursor). The unreacted secondreagent is then purged.

It is determined whether another ALD deposition cycle is to beperformed. A typical ALD cycle may form a layer that is 0.05 nm, forexample. To form a 0.5 nm hafnium oxide layer, 10 cycles would need tobe performed. So, if it is determined that the desired number of cycleshas been performed or that the desired thickness has been reached, theprocess continues. If more ALD cycles need to be completed, the sequenceis repeated.

In operation 630, a hafnium oxide layer is formed using ALD process withthe hafnium precursor together with an oxygen-containing oxidant, suchas ozone, plasma oxygen, or water. The excess (unreacted portion) of thefirst reagent is purged, for example by purging the ALD chamber toremove excess precursor.

A second reagent is introduced to the substrate. The second reagentcombines with the first reagent to form the hafnium oxide. The secondreagent is an oxygen-containing oxidizer, for example ozone gas, plasmaoxygen gas, or water vapor. In some embodiments, the same oxidant of theALD hafnium oxide process is used. The second reagent forms an oxide ofthe hafnium metal contained in the first reagent (the precursor). Theunreacted second reagent is then purged.

It is determined whether another ALD deposition cycle is to beperformed. A typical ALD cycle may form a layer that is 0.5 Å, forexample. To form a 2 nm hafnium oxide layer, 40 cycles would need to beperformed. So, if it is determined that the desired number of cycles hasbeen performed or that the desired thickness has been reached, theprocess continues. If more ALD cycles need to be completed, the sequenceis repeated.

FIG. 7 illustrates an illustrative flowchart for forming a semiconductordevice according to some embodiments of the present invention. Thedescribed flowchart is a general description of techniques used to formthe semiconductor device described above. The flowchart describestechniques for forming a semiconductor device generally including a gatestack disposed on a semiconductor channel between a source and a drain.Although certain processing techniques and specifications are described,it is understood that various other techniques and modifications of thetechniques described herein may also be used.

In operation 700, a silicon-containing substrate is provided. Inoperation 710, a gate dielectric is formed on the substrate. Thesubstrate is first prepared for ALD process, for example, heated to atemperature less than or equal to about 400 C. After preparing thesubstrate, an erbium oxide layer is formed using ALD process, followedby a hafnium oxide layer. For example, a first few cycles of the ALDprocess, e.g., less than 20 cycles, is used to form the erbium oxidelayer, utilizing an erbium precursor together with an oxidant. The lastcycles of the ALD process is used to form the hafnium oxide layer,utilizing a hafnium precursor together with an oxidant. The ALD processcan be a standard ALD process as discussed above, including sequentiallyintroducing and purging the precursor and the oxidant to form the erbiumoxide and hafnium oxide layers.

In operation 720, other processes are performed to complete thesemiconductor device, including depositing a gate electrode, a gateconductor, patterning the gate dielectric and the gate electrode andconductor, forming source and drain regions, and forming spacer. Deviceinterconnection can also be included.

Although the foregoing examples have been described in some detail forpurposes of clarity of understanding, the invention is not limited tothe details provided. There are many alternative ways of implementingthe invention. The disclosed examples are illustrative and notrestrictive.

What is claimed is:
 1. A semiconductor device, comprising asilicon-containing substrate; a gate dielectric layer disposed on thesubstrate, wherein the gate dielectric layer comprises a hafnium oxidelayer disposed on an erbium oxide layer; a gate electrode layer disposedon the gate dielectric layer.
 2. A device as in claim 1 wherein theerbium oxide layer is formed by a first ALD process comprising an erbiumprecursor and an oxidant.
 3. A device as in claim 2 wherein the firstALD process for depositing the erbium oxide layer comprises betweenabout 5 to 10 ALD cycles.
 4. A method as in claim 3 wherein the erbiumprecursor comprises one of an erbium cyclopentadienyl complex or anerbium beta-diketonate chelate.
 5. A method as in claim 3 wherein theerbium precursor comprises one or more of tri(cyclopentadienyl) erbium(Er(Cp)₃), tri(methylcyclopentadienyl) erbium (Er(MeCp)₃),tri(ethylcyclopentadienyl) erbium (Er(EtCp)₃),tri(isopropylcyclopentadienyl) erbium (Er(IpCp)₃),tri(nbutylcyclopentadienyl) erbium (Er(nBuCp)₃), andtris-tetramethylheptanedionate erbium (Er(thd)₃).
 6. A device as inclaim 1 wherein a thickness of the erbium oxide layer is less than about1 nm.
 7. A device as in claim 1 wherein the hafnium oxide layer isformed by a second ALD process comprising a hafnium precursor and anoxidant.
 8. A method as in claim 7 wherein the hafnium precursorcomprises one or more of hafnium chloride (HfCl₄), hafnium iodine(Hfl₄), or anhydrous hafnium nitrate (Hf(NO₃)₄).
 9. A method as in claim7 wherein the hafnium precursor comprises one or more oftetrakis(dialkylamino) hafnium, tetrakis(dimethylamino) hafnium((Me₂N)₄Hf or TDMAH), tetrakis(diethylamino) hafnium ((Et₂N)₄Hf orTDEAH), or tetrakis(ethylmethylamino) hafnium ((EtMeN)₄Hf or TEMAH). 10.A method as in claim 7 wherein the second ALD process for depositing thehafnium oxide layer comprises between about 5 to 20 ALD cycles.
 11. Adevice as in claim 1 wherein a thickness of the hafnium oxide layer isless than about 2 nm.
 12. A device as in claim 1 further comprisingsource and drain regions disposed on the substrate.
 13. A device as inclaim 1 wherein the erbium oxide layer and the hafnium oxide layer areformed in situ in a same process chamber.
 14. A device as in claim 1,wherein the gate electrode comprises one of Al, polysilicon, TiN, TaN,HfN, RuN, WN, W, MoN, TaSiN, RuSiN, WSiN, HfSiN, or TiSiN.